Allylic halogenation of unsaturated amino acids.

نویسندگان

  • Christopher J Easton
  • Alison J Edwards
  • Stephen B McNabb
  • Martin C Merrett
  • Jenny L O'Connell
  • Gregory W Simpson
  • Jamie S Simpson
  • Anthony C Willis
چکیده

A range of dehydro amino acid derivatives has been prepared and subjected to halogenation using either molecular bromine or chlorine, or NBS. Allylic halogenation of the unsaturated amino acid side chains occurs through radical bromination with NBS. The procedure is complementary to treatment with chlorine, which also affords allyl halides. This latter and unusual reaction is shown through a deuterium labelling study to proceed via an ionic mechanism. The choice of NBS or chlorine for allyl halide synthesis is shown to depend on the potential to avoid competing reactions, such as halolactonization of leucine derivatives with chlorine, and hydrogen abstraction and bromine incorporation at multiple sites on treatment of isoleucine derivatives with NBS. The synthetic utility of the allyl halides prepared in this study is indicated through the synthesis of a cyclopropyl amino acid derivative and the extension of the carbon skeleton of an amino acid side chain.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Regioselective and diastereoselective allylic amination using chlorosulfonyl isocyanate. A novel asymmetric synthesis of unsaturated aromatic 1,2-amino alcohols.

The diastereoselective synthesis of unsaturated aromatic 1,2-amino alcohols can be achieved on an epimeric mixture of optically active allylic ethers having a hydroxyl group attached to an allylic chiral center to the pi-system using chlorosulfonyl isocyanate. These reactions produced the unsaturated anti-1,2-amino alcohols either exclusively or predominantly only for aromatic derivatives. The ...

متن کامل

Carbonylative coupling of allylic acetates with aryl boronic acids.

The first allylic carbonylation reaction of allylic acetates with aryl boronic acids under carbon monoxide has been developed. Using Pd-PCy3 as a catalyst, a wide spectrum of allylic acetates was carbonylated in the presence of various aryl boronic acids, affording α,β-unsaturated aryl ketones in good to excellent yields. Preliminary studies indicate that carbon monoxide always inserts at the l...

متن کامل

Tandem regio- and diastereo-selective synthesis of halogenated C-vinyl glycosides from unactivated arylacetylenes.

A highly regio- and diastereo-selective synthesis of halogenated C-vinyl glycosides has been achieved from glycals and unactivated aryl acetylenes in the presence of halogenated Lewis acids via a tandem glycosylation-halogenation reaction. The Lewis acid used served the dual purpose of activating the allylic acetoxy group of glycals and serving as halogen source for Markovnikov addition across ...

متن کامل

Determination of the fatty acid profile by 1H-NMR spectroscopy

The common unsaturated fatty acids present in many vegetable oils (oleic, linoleic and linolenic acids) can be quantitated by 1H-nuclear magnetic resonance spectroscopy (1H-NMR). A key feature is that the signals of the terminal methyl group of linolenic acid are shifted downfield from the corresponding signals in the other fatty acids, permitting their separate integration and quantitation of ...

متن کامل

The synthesis of chiral β-aryl-α,β-unsaturated amino alcohols via a Pd-catalyzed asymmetric allylic amination.

Chiral β-aryl-α,β-unsaturated amino alcohols were synthesized via a Pd-catalyzed asymmetric allylic amination of 4-aryl-1,3-dioxolan-2-one using planar chiral 1,2-disubstituted ferrocene-based phosphinooxazolines as ligands. Under the optimized reaction conditions, a series of substrates were examined and the products were obtained in good to excellent yields (up to 92%) and enantioselectivitie...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Organic & biomolecular chemistry

دوره 1 14  شماره 

صفحات  -

تاریخ انتشار 2003